JPH03126770A - Dispersion solution of polymer fine particles - Google Patents

Abstract

PURPOSE:To provide the subject dispersion solution having highly improved sagging resistance on a vertical surface, etc., by copolymerizing and crosslinking a vinylic monomer mixture in the presence of a mixture of two kinds of specific macromonomers in a specified organic solvent. CONSTITUTION:The objective dispersion solution is prepared by copolymerizing and crosslinking a vinylic monomer mixture (C) in an organic solvent not dissolving the produced polymer, in the presence of a mixture of (A) a macromonomer containing the molecular chain of a poly(12-hydroxystearic acid) and having one or more polymerizable unsaturated double bonds per molecule and (B) a macromonomer comprising the copolymer of an ethylenic unsaturated monomer and having a solubility parameter of 7.5-9.2 and on the average 1.0-1.5 polymerizable double bond per molecule. The vinylic monomer mixture (C) contains >=0.5wt.% of >= two kinds of vinylic monomers having complemental functional groups capable of combining with the components A and B, respectively.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention provides a method for stably dispersing a mixture of a macromonomer having a molecular chain of poly(12-hydroxystearic acid) and a macromonomer having a specific solubility parameter. The present invention relates to a dispersion of gelling polymer fine particles used as an agent, and a curable resin composition containing the dispersion.

[Prior art and its problems] As a method for producing fine polymer particles stably dispersed with a polymer dispersion stabilizer in an organic solvent mainly composed of aliphatic hydrocarbons (so-called non-aqueous polymer dispersion), Various methods have been proposed (for example, Japanese Patent Publication No. 57-48566, Japanese Patent Publication No. 57-34846
(See Japanese Patent Application Laid-Open No. 161431/1984, etc.).

These methods include a first segment that is solvated in an organic solvent and a second segment that is substantially unsolvated in the organic solvent and becomes associated with or anchored to the dispersed polymer particles. This method consists of first forming dispersed polymer particles in the presence of a partial stabilizer consisting of segments of , and then crosslinking the particles.

A typical example of the above-mentioned dispersion stabilizer is the graft polymerization or block polymerization of a non-solvated component, which is a polymer chain mainly composed of methyl methacrylate, to a solvated component, which is a self-condensation product of 12-hydroxystearic acid. Things can be mentioned.

In addition, in JP-A-61-195008, it is stated that the hydroxyl group or carboxyl group of the 12-hydroxystearic acid self-condensate which becomes the solvate component, rather than the polymer, is transferred from the two segments to the block or graph 1. A macromonomer in which an average of about 1.0 polymerizable unsaturated bonds per molecule are introduced by reacting the group with a polymerizable unsaturated monomer having a functional group such as an epoxy group or an isocyanate group. A method has been proposed in which a dispersion stabilizer is used as it is to produce a polymer fine particle dispersion.

Furthermore, copolymers of hinyl monomers having a specific composition that are soluble in organic solvents mainly composed of aliphatic hydrocarbons (for example, acrylic copolymers with a solubility parameter of 9.0 or less) have a A method for producing a polymer fine particle dispersion using a macromonomer having an average of about 1.0 polymerizable double bonds per molecule as a dispersion stabilizer has also been proposed (Japanese Patent Application Laid-Open No. 1983-1993).
-177068, Japanese Patent Publication No. 59-33032, Japanese Patent Application Laid-Open No. 61-278573, etc.).

These polymer particles (dispersions) are used in paints, adhesives, etc. in combination with crosslinking agents such as amino resins and polyisocyanate compounds, and if necessary, acrylic resins, polyester resins, alkyd resins, etc.

The roles and functions of polymer particles in these systems, especially in paints, include: 1) high solidity differentiation; 2) improvement of physical properties of paint films such as weather resistance and mechanical properties; and 3) structural viscosity (thixotropy) in paints. Examples include imparting (i. lobby property) and improving pigment orientation and shearing (sagging) resistance.

By the way, the two conventional types of polymer fine particles mentioned above, namely, the type using a dispersion stabilizer containing a 12-hydroxystearic acid self-condensate as a solvating component (hereinafter referred to as r
P-12H3A type (sometimes abbreviated as "P-12H3A type") and a type using a dispersion stabilizer containing a copolymer of vinyl monomers with a specific composition as a solvating component (hereinafter referred to as "vinyl copolymer type"). (sometimes abbreviated as), there are major differences between the two. For example, the P-12H3A type has a great effect of imparting structural viscosity to the system, and can be used to improve the orientation of metal flake pigments such as aluminum flakes in metallic base enamel paints by simply adding a small amount of polymer particles. On the other hand, with Totubu Coat paints, although the sagging resistance can be improved, the gloss of the resulting painted surface is extremely reduced and the smoothness is significantly impaired. The current situation is that it is virtually impossible to add it to top coat paints.

On the other hand, when a vinyl copolymer type is added to a paint, it can improve the physical properties of the paint film without substantially reducing the gloss of the resulting paint surface and without deteriorating the finished appearance such as smoothness. Since the effect of imparting structural viscosity to the paint is not sufficient, there is a problem that the effect of improving the orientation and sagging resistance of the metal flake pigment is small.

Moreover, even if the above two types of polymer fine particles are used together,
It is difficult to achieve both sagging resistance and high gloss and smoothness of the coated surface.

The state of dispersion of fine polymer particles within a paint system is determined by the balance between dispersion force (repulsion) and cohesive force (attraction) acting between particles, and in the case of fine polymer particles whose surface is covered with a dispersion stabilizer polymer. It is known that the dispersion force and cohesive force vary greatly depending on the solubility of the dispersion stabilizer polymer. That is, in a solvent that is a good solvent for the dispersion stabilizer polymer, the polymer molecules are sufficiently spread and form a three-dimensional repellent layer on the particle surface, which acts to prevent particle association and aggregation. On the other hand, in a poor solvent, the molecules of the dispersion stabilizer polymer are contracted, the steric repulsion is weakened, and the dispersion stabilizer polymers tend to aggregate with each other, resulting in aggregation of the polymer particles.

As described above, the stability of polymer particles dispersed in an organic solvent is greatly influenced by the solubility of the dispersion stabilizer polymer in the solvent.

The above relationship is the same in a paint system consisting of polymer fine particles/base resin/crosslinking agent/solvent; when the paint is applied and the solvent evaporates, it is continuous with the dispersion stabilizer polymer on the surface of the polymer fine particles. The degree of dispersion and aggregation of the polymer fine particles in the coating liquid or coating film are greatly influenced by the degree of compatibility with the base resin and the crosslinking agent forming the phase.

Looking at the two types of polymer fine particles mentioned above, I
In the 2-H5A type, the dispersion stabilizer uses a self-condensate of 12-hydroxystearic acid as a solvating component, and this type can be used for ordinary paints such as acrylic polymers, polyester polymers, alkyd polymers, Polyisocyanate compounds and amide resins such as melamine/formaldehyde resins and urea/formaldehyde resins are incompatible, so in paints containing P-12-H5A type, as the solvent evaporates, the dispersion stabilizer polymer becomes a continuous phase. Phase separation occurs from the polymer (base resin/crosslinking agent), and the polymer particles associate or aggregate.This increases the structural viscosity and improves sagging resistance and pigment orientation. This results in significantly inferior gloss and smoothness.On the other hand, in the vinyl copolymer type, the dispersion stabilizer is a copolymer of vinyl monomers, so it is generally It has very good compatibility with crosslinking agents such as
Even in state 0 of the coating liquid or coating film in which the solvent has evaporated, the polymer particles cannot associate with each other. Therefore, although the coated surface has excellent gloss and smoothness, it cannot impart structural viscosity and cannot improve sagging resistance when painting vertical surfaces.

[Means to Solve the Problem] The inventors of the present invention have found that it is possible to stably achieve an appropriate degree of agglomeration, and to improve sagging resistance and metal flexure without adversely affecting the high gloss and smoothness of the painted surface. As a result of intensive research in order to obtain polymer particles that can significantly improve the orientation of pigments and improve the physical properties of coating films, we have found that two specific types of dispersion stabilizers are used, and the internal The present inventors have discovered that the above object can be achieved by using crosslinked gelled polymer particles, and have completed the present invention.

Thus, the present invention provides a macromonomer containing a molecular chain of poly(12-hydroxystearic acid) and having an average of about 1 or more polymerizable unsaturated double bonds per molecule (
A) and an ethylenically unsaturated monomer copolymer,
A macromonomer (B ), each containing at least 0.5% by weight of at least two vinylic monomers each having complementary functional groups capable of reacting and bonding with each other. The mixture is dissolved in an organic solvent in which the macromonomer (A), the macromonomer (B), and the vinyl monomer mixture are dissolved, but the polymer formed from the vinyl monomer mixture is not substantially dissolved. The present invention provides a dispersion of gelled polymer particles obtained by copolymerization and crosslinking reaction.

The present invention also provides: (i) the above-mentioned gelling polymer fine particle dispersion; (ii)
A base resin forming a continuous phase that is incompatible with the macromonomer (A) but compatible with the macromonomer (B), and (out) at least one crosslinking agent selected from amine resins and polyisocyanate compounds. Curing resin containing 1! The present invention will be described in more detail below.

The gelled polymer fine particle dispersion of the present invention is used as a total dispersion stabilizer for a mixture of macromonomer (A) and macromonomer (B), and is copolymerized with a vinyl monomer mixture in a specific organic solvent. and those obtained by crosslinking reaction.

The macromonomer (A) contains a molecular chain of poly(12-hydroxystearic acid) (hereinafter sometimes abbreviated as "P l 2H3AJ") and a polymerizable unsaturated double bond, and contains the above-mentioned P- The number average molecular weight of 12H5A is preferably within the range of 1,000 to 3,000, and more preferably within the range of 1,500 to 2,200.

In the present invention, "macromonomer J" means a polymer having a polymerizable unsaturated double bond in the polymer molecule.

The macromonomer (A) typically includes two types, and the first type has a functional group capable of reacting with at least one of these three groups on the terminal carboxyl group or hydroxyl group of P-12H3A. It is a reaction product in which about 1 or more, preferably about 1, polymerizable unsaturated group is introduced per molecule by reacting a polymerizable unsaturated compound. Such reaction products are, for example, (])
P-], to the terminal carboxyl group of 2H'SA, glycidyl acrylate, glycidyl methacrylate, allyl glycyl ether, (3,4-r-poquincyclohexyl)methyl methacrylate, (3,4-epoxycyclohexyl)methyl acrylate, etc. Adding an unsaturated monomer containing a monoepoxy group in the presence of a catalyst such as a tertiary amine; or (2) adding inanate ethyl acrylate or isocyanate ethyl to the terminal carboxyl group or secondary hydroxyl group of P-12H5A. methacrylate, m-
It can be produced by a method such as reacting an unsaturated monomer containing a monoisocyanate group such as an equimolar adduct of 1'-sopropenyl-α,σ-dimethylbenzyl isocyanate or a diisocyanate compound and hydroxyalkyl acrylate or hydroxyalkyl methacrylate. 14 I can. In addition, when producing a macromonomer by the latter method (2), two or more polymerizable double bonds may be introduced into the molecule.

Preferably, the first type of macromonomer contains on average about 1.0 polymerizable double bonds per molecule;
If more polymerizable double bonds are introduced, there is a risk that the entire reaction system will gel during the production of gelling polymer particles. Therefore, in the method of item 1 (2), for example,
P-12H5A 1 .

It is desirable to react about 1.0 mol of the isocyanate group-containing unsaturated monomer with respect to 0 mol.
About 1.0 double bonds can be selectively introduced into the secondary hydroxyl group in P-12H5A. In addition, if the number of polymerizable double bonds introduced per I molecule is less than about 1.0 on average per molecule, the grafting rate to the particle surface will be small, resulting in particle consolidation and raw skin. Particle stability may deteriorate. In the production of the macromonomer, known polymerization inhibitors and, if necessary, a tertiary polymer are usually used.
Catalysts such as dibutyltin dilauryl amines or dibutyltin dilauryl amines can be used.

The second type of macromonomer (A) is a graft polymer or block polymer having a polymerizable unsaturated group, and includes a solvated portion such as P-12ISA and methyl methacrylate-1. Macromonomers having two segments with a non-solvated portion that is a copolymer of a polymerizable unsaturated monomer mixture mainly composed of highly polar monomers, which can be a comb-shaped copolymer, are included. Ru.

Such a macromonomer is obtained by adding, for example, a polymerizable unsaturated monomer having an epoxy group to a reaction product in which about one polymerizable unsaturated group is introduced per molecule, which is obtained by methods such as (1) and (2) above. and a polymerizable unsaturated monomer that does not have a group that reacts with an epoxy group to a copolymer obtained by graft polymerization or block polymerization, which has a carboxyl group that reacts with an epoxy group in this copolymer. [6] obtained by reacting a polymerizable unsaturated compound to introduce an average of about 1 or more, preferably about 1 to 10, more preferably 4 to 7 polymerizable unsaturated groups per molecule. can. Examples of the polymerizable unsaturated monomer having an epoxy group include glycidyl acrylate,
Examples include glycidyl methacrylate, allyl glycidyl ether, (3,4-epoxycyclohexyl)methyl methacrylate, (3,4-epoxycyclohexyl)methyl acrylate, and the like. Examples of the polymerizable unsaturated compound having a carboxyl group that reacts with an epoxy group include acrylic acid, methacrylic acid, crotonic acid, and half esters of maleic acid or fumaric acid. In order to introduce a polymerizable unsaturated group by reacting an epoxy group in a copolymer with a polymerizable unsaturated compound having a carboxyl group, for example, a method of adding both in the presence of a catalyst such as a tertiary amine etc. Conventionally known methods such as can be used.

Furthermore, examples of the polymerizable unsaturated group having no group that reacts with the epoxy group include those listed below.

(a) Esters of acrylic acid or methacrylic acid: for example, methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate, lauryl acrylate, methyl methacrylate, C1-18 alkyl esters of acrylic acid or methacrylic acid such as ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, hexyl methacrylate, octyl methacrylate, lauryl methacrylate; acrylic acid such as allyl acrylate and allyl methacrylate or C2-8 allenyl ester of methacrylic acid; C2-8 hydroxyalkyl ester of acrylic acid or methacrylic acid such as hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxyethyl acrylate;
03-1 of acrylic acid or methacrylic acid such as allyloxyethyl acrylate and allyloxine methacrylate
8 alkenyloxyalkyl ester, etc.

(b) Vinyl aromatic compounds: for example, styrene, σ
-Methylstyrene, vinyltoluene, p-chlor8 styrene, vinylpyridine, etc.

(C) Others: Acrylonitrile, methacrylonitrile, methyl isopropenyl ketone: vinyl acetate, Beoba monomer (Shell Chemicals), vinyl globionate, vinyl vivalate, etc.

Among these vinyl monomers, particularly preferred are the esters of acrylic acid or methacrylic acid (a), particularly highly polar monomers such as methyl methacrylate. It is desirable that the highly polar monomer such as methyl methacrylate accounts for at least 50% by weight of the polymerizable unsaturated monomer mixture to be subjected to polymerization.

Polymerization of the above monomer mixture uses a radical polymerization initiator,
This can be carried out according to radical polymerization methods known per se. Examples of usable radical polymerization initiators include 2,2'-azobisisobutyronitrile, 2,2'-
Examples include azo initiators such as azobis (24-dimethylvaleronitrile); peroxide initiators such as benzoyl peroxide, lauryl peroxide, and tert-butyl peroctoate; these polymerization initiators are generally used in polymerization. It can be used in an amount of 0.5 to 10 parts by weight, preferably 0.3 to 3 parts by weight, per 100 parts by weight of the monomer mixture.

The second type of macromonomer (A) is most preferably a combination of an epoxy group-containing polymer and a polymerizable unsaturated compound having a carboxyl group (epoxy group/carboxyl group) from the viewpoint of ease of reaction. In addition, combinations of hydroxy group-containing polymers and polymerizable unsaturated compounds having isocyanate groups (hydroxyl groups/isocyanate groups), combinations of epoxy group-containing polymers and polymerizable unsaturated compounds having amino groups (epoxy groups/amino combinations such as combinations of isocyanate group-containing polymers and polymerizable unsaturated compounds having amino groups (isocyanate groups/amino groups), and replacement of reactive groups between polymers and polymerizable unsaturated compounds in these combinations. It can also be obtained by a combination of

The macromonomer (B) is a copolymer of 0 ethylenically unsaturated monomers, and has a solubility parameter (SP value) in the range of 7.5 to 9.2, preferably 8.0 to 9.0. and has an average of about 1.0 to about 15 polymerizable unsaturated double bonds per molecule. Moreover, the macromonomer (B) has a number average molecular weight of 3,000 to 20,0
It is preferably within the range of 00, especially 4,000 to
It is more preferable that the hydroxyl value is within the range of 10,000, and furthermore, the hydroxyl value is within the range of 45-15045-15O/g when the gelling polymer fine particles are blended into the paint. Particularly preferred in terms of reactivity with crosslinking agents such as isocyanate compounds, 50-
Even more preferably it is within the range of 120 mg-KOH/g. If the S-P value of the macromonomer (B) is less than 7.5, when the raw skin gelling polymer fine particles are blended into other resins, they are difficult to be compatible with the base resin and crosslinking agent that form the continuous phase. On the other hand, if it exceeds 92, not only will the compatibility with the base resin forming the continuous phase decrease, but it will also become insoluble in solvents mainly composed of aliphatic hydrocarbons. It no longer plays the role of a stabilizer.

In the present invention, the "solubility parameter (SP value)" is a value theoretically calculated by the following formula.

SP value: δ δX100 = (δ, XA) + (δ, xB) + (δ.xC
) 10. . . . . , C...: Monomer 1, I... weight% in the copolymer) Furthermore, the macromonomer (B) has an average content of about 1 per molecule.
．． It has 0 to about 1.5 polymerizable unsaturated double bonds, and if the number of polymerizable unsaturated double bonds is less than about 1.0, when producing the polymer fine particle dispersion, , the grafting efficiency of the macromonomer (B) to the particle polymer decreases, and there is a tendency for particle aggregation to occur and the stability of raw-shelled particles to deteriorate22. and,
The entire system becomes thicker and tends to gel.

The macromonomer (B) is, for example, (1) mainly composed of long-chain alkyl esters of acrylic acid or methacrylic acid such as octyl acrylate, lauryl acrylate, stearyl acrylate, octyl methacrylate, lauryl methacrylate, or lauryl methacrylate. copolymerization of a vinyl monomer containing a carboxyl group such as acrylic acid or methacrylic acid, and optionally a vinyl monomer containing a hydroxyl group such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxyalkyl acrylate, or hydroxypropyl methacrylate. After that, a polymer having a side chain double bond obtained by reacting the carboxyl group of the copolymer with glycidyl acrylate or glycidyl methacrylate.
(2) In (1) above, after copolymerizing using glycidyl acrylate 3 or glycidyl methacrylate instead of the carboxyl group-containing vinyl monomer, the glycidyl groups of the copolymer are reacted with acrylic acid or methacrylic acid. (3) The above-mentioned vinyl monomer mainly consisting of a long-chain alkyl ester of acrylic acid or methacrylic acid, the above-mentioned hydroxyl group-containing vinyl monomer, and, if necessary, a carboxyl group. After copolymerizing the containing vinyl monomers, isocyanate ethyl acrylate, isocyanate ethyl methacrylate, m-impropenyl-α, α-dimethylbenzyl isocyanate or a diisocyanate compound and hydroxyalkyl acrylate or hydroxyalkyl methacrylate are added to the hydroxyl groups of the copolymer. Examples include polymers having side chain double bonds obtained by reacting monoisonanate group-containing unsaturated monomers such as equimolar adducts. In addition, another method for introducing a double bond at the end of a polymer is to use γ, γ'-azobis-γcyanovaleric acid as an initiator and monomer A method of introducing a carboxyl group at the end of the body and adding glycidyl (meth)acrylate to this: or γ, γ′-
Examples include a method in which a hydroxyl group is introduced at the end of a polymer using a combination of azobis (γ-cyano n-pentanol) and 2-mercaptoethanol, and then an isocyanate group-containing monomer is added.

In the gelling polymer fine particle dispersion of the present invention, the vinyl monomer mixture forming the fine particles is composed of at least two types of vinyl monomers each having complementary functional groups that can react with each other and bond with each other. It is a vinyl monomer mixture containing. Examples of combinations of complementary functional groups that can react and bond with each other in such a vinyl monomer mixture include (i) epoxy group/carboxyl group (U) hydroquinyl group/isocyanate group (iii) epoxy Group/amino group 5 (iv) Isocyanate group/amino group (V) Alcoquinyl group/hydroxyl group (vi) Combinations such as epoxy group/phosphoric acid group can be mentioned. Specific examples of such combinations of two or more vinyl monomers each having complementary functional groups that can react and bond with each other include the following: (i) Examples of (i) include combinations of epoxy group-containing monomers such as glycidyl acrylate and glycidyl methacrylate with carboxyl group-containing monomers such as acrylic acid and methacrylic acid; examples of (i) include hydroxyethyl acrylate and hydroxy Hydroxyl group-containing monomers such as ethyl methacrylic acid, isocyanate ethyl acrylate or isocyanate ethyl methacrylate, m-isogropenyl σ
, a-dimethylbenzylisocyanate, inphorone diisocyanate/hydroxyethyl acrylate or hydroxyethyl methacrylate equivalent adduct, and other isonene6-containing monomers.

An example of (iii) is a combination of the above epoxy group-containing monomer and an aminoalkyl acrylate or aminoalkyl methacrylate monomer; an example of Ov) is a combination of the above isocyanate group-containing monomer and an aminoalkyl acrylate monomer; Combination with aminoalkyl acrylate or aminoalkyl methacrylate monomer: Examples of (v) include the above hydroxyl group-containing monomer and an alkoxysilyl group-containing monomer such as γ-methacryloyloxybrobyl methacrylate. The combination of (vl
) Examples include combinations of the above epoxy group-containing monomers and phosphoric acid group-containing monomers such as acid phosphooxyethyl (meth)acrylate.

Among these combinations, (i), (ii), (v) and (vi) are preferred, with (i) being particularly preferred.

Intra-particle crosslinking is carried out by the above-mentioned reaction between complementary functional groups, but in order to promote particle cross-linking, a small amount of multi-vinyl monomer is added in addition to the monomer having the above-mentioned complementary functional groups. May be used. Multi-vinyl monomers are vinyl monomers containing at least two polymerizable double bonds in one molecule, such as divinylbenzene, ethylene glycol diacrylate, isocyanate ethyl acrylate/hydroxyethyl acrylate, or Examples include hydroxyethyl methacrylate adducts.

At least two types of vinyl monomers each having the above-mentioned complementary functional groups are present in the vinyl monomer mixture in an amount of at least 0.5% by weight or more, preferably within a range of 0.5 to 20% by weight. The polyvinyl monomers may also be present in the vinyl monomer mixture at a concentration of less than 5.0% by weight. These vinyl monomers are components for crosslinking the prepared polymer particles, and the amount and type of vinyl monomers used, the combination of monomers, etc. can be determined as desired depending on the desired performance of the product polymer particles. can be selected.

The vinyl monomer mixture forming the fine particles may contain, in addition to the above-mentioned crosslinking monomer, at least one other copolymerizable vinyl monomer. Other vinyl monomers that can be used include 8. There is no particular restriction as long as it is a radically polymerizable unsaturated monomer, and various types can be used, but typical examples include 2. Examples of monomers for producing the macromonomer (A) having two segments include polymerizable unsaturated monomers selected from the above-mentioned polymerizable unsaturated monomers (a), (b) and (c).

Among these other vinyl monomers, particularly preferred are esters of methacrylic acid or acrylic acid, with methyl methacrylate being particularly preferred. In addition, these other vinyl monomers that can be used account for at least 50% by weight of the vinyl monomer mixture to be subjected to polymerization.
It is desirable that the total number of employees be at least the same.

Macromonomer (A) in gelling fine particle polymer production
and the macromonomer (B), the solid content weight ratio (A)/(B) is 70/30 to 20/80, especially 50
It is preferable that the ratio is within the range of 150 to 25/75 from the viewpoint of achieving both the anti-sagging effect and the gloss and smoothness of the coated surface. Furthermore, the ratio between the amount of dispersion stabilizer, which is the sum of macromonomers (A) and 9 (B), and the amount of the vinyl monomer mixture forming the particles is such that the dispersion stabilizer/monomer mixture is 1 O/ 90~60/40, especially 20/80~
40/60 coverage is preferred. When the amount of dispersion stabilizer is small, coarse particles tend to be generated during dispersion particle polymerization, and the stability of the dispersion liquid tends to be poor. On the other hand, when the amount of dispersion stabilizer is large, Small particle size (0
, 06 μm or less), and the anti-sagging effect tends to be insufficient.

Although the produced dispersed polymer particles are not substantially dissolved in the organic liquid used as a dispersion medium when producing the dispersion liquid of the polymer fine particles of the present invention, the macromonomer (A) which is the dispersion stabilizer, (B) and the vinyl monomer mixture include organic liquids that are substantially immiscible with water and serve as good solvents. Preferred specific examples of such organic liquids include:
Examples include petroleum aliphatic hydrocarbons such as hexane, heptane, octane, and mineral spirits. Each of these can be used alone or with other relatively less polar organic solvents (e.g. toluene, xylene,
butyl acetate). When used as a mixed solvent, it is highly desirable that the petroleum-based aliphatic hydrocarbons account for at least 60% by weight of the solvent mixture.

The copolymerization of the vinyl monomer mixture in the organic liquid in the presence of the macromonomer according to the present invention can be carried out using methods known per se (for example, the method described in JP-A-57-177068). The reaction temperature during polymerization can generally be in the range of 60 to 160°C, and the reaction can usually be completed in 4 to 8 hours.

As a method for preparing crosslinked gelled polymer fine particles of the present invention, for example, dispersed polymer particles are formed in advance, and then a third
A method of performing a crosslinking reaction by complementary functional groups within dispersed polymer particles using a tertiary amine catalyst, or a method in which a tertiary amine catalyst is mixed in advance into a vinyl monomer mixture or an organic liquid and the dispersion polymer is It is possible to use a method in which a crosslinking reaction within the polymer particles is carried out in parallel with the polymerization reaction that forms the aggregate particles, but in the latter case, the vinyl monomers in the reaction system are It is desirable to reduce the concentration of the polymer mixture compared to the former method.

The tertiary amine catalyst used as the reaction catalyst between the complementary functional groups described above is not particularly limited, and includes, for example, dimethylaminoethanol, diethylaminoethanol, N,
N-dimethyl-〇-dodecylamine and the like can be mentioned. Furthermore, when intraparticle crosslinking is performed by a combination of an isocyanate group-containing monomer and a hydroxyl group-containing monomer, a tin-based catalyst or the like may be used as necessary.

The important requirements for the polymerization reaction in the method of the invention are that the monomer concentration in the organic liquid be low and that the interparticle distances of the dispersed polymer particles being formed be sufficiently large. Therefore, in order to accelerate the polymerization rate of the monomer, it is necessary to provide sufficient temperature necessary for decomposing the polymerization initiator and to appropriately control the monomer supply rate. is important. However, if the monomer concentration in the reaction system becomes extremely high, there is a risk that the entire system will gel.

Regarding the latter requirement, it is important to keep the concentration of the dispersed polymer particles formed above a certain level.
Specifically, it is desirable to complete the polymerization reaction while suppressing the concentration of the dispersed polymer particles formed to be 40% by weight or less, preferably 30% by weight or less. When the concentration of dispersed polymer particles exceeds 40% by weight, they generally tend to gel or become coarse particles.

In addition, when using monomers in which the combination of complementary functional groups is incyaneto group/hydroxyl group or phosphoric acid group/epoxy group, if each monomer is mixed in the same tank,
Before dropping into the reaction tank, there is a risk that the divinyl monomer will react and cause gelation during particle synthesis or produce coarse particles, so it is better to mix them in separate tanks.

Also, as a matter of course, when crosslinking particles using a combination of isocyanate group-containing monomer/hydroxyl group-containing monomer, a solvent that reacts with isocyanate groups, such as an alcohol-based solvent, should be used as the reaction medium. isn't it.

The curable resin composition of the present invention includes: (1) the above gelatinized polymer fine particle dispersion, (iJ)
Contains a base resin forming a continuous phase that is incompatible with the macromonomer (A) but compatible with the macromonomer (B), and (iii) at least one crosslinking agent selected from amino resins and polyisocyanate compounds. By incorporating the dispersion liquid (i) into the system, the composition of the present invention improves sagging resistance and pigment content without adversely affecting the gloss and smoothness of the painted surface. The orientation can be significantly improved.

The base resin (0) forming the above-mentioned continuous phase is not compatible with the macromonomer (A), but the macromonomer (B
) is compatible with (iii) a cross-linking agent and can be cured to achieve the desired performance other than sag resistance. For example, acrylic resin, polyester resin, alkyd resin, etc. can be used. When the composition of the present invention is used as a top coat, the composition has a number average molecular weight of 3.000 to 50,000 and a solubility parameter of 7.5.
-9,5 and a hydroxyl value within the range of 45-170 mgKOH/g are particularly preferred.

The above-mentioned acrylic resin is an ethylenic resin mainly composed of an ester of acrylic acid or methacrylic acid in an organic solvent such as an aromatic hydrocarbon type, ester type, ether type, ketone type, alcohol type, or aliphatic hydrocarbon type. Examples include those obtained by polymerizing saturated monomers by known methods. As the polymerization method, a solution radical polymerization method using a polymerization initiator is generally used. As ethylenically unsaturated monomers that polymerize,
The epoxy group used in the production of the second type of macromonomer (A) and the monomers exemplified in (a), (b) and (C) above as polymerizable unsaturated monomers that do not have a reactive group; Regarding the production of Type 1 Mac50 monomer (A), the monoepoxy group-containing unsaturated monomers exemplified in (1) above, such as nialic acid, methacrylic acid, crotonic acid, and half esters of maleic acid or fumaric acid, etc. Examples include polymerizable unsaturated compounds containing carboxyl groups.

In the present invention, the compatibility between the macromonomers (A) and (B) and the base resin (ij) forming the continuous phase can be determined by the following method.

The macromonomer and the base resin are blended and mixed at a solid content weight ratio of 1/l, and coated on a glass plate to a thickness of about 100 μm after evaporating the solvent.
The solvent is evaporated at a temperature of 30°C until the amount of solvent remaining in the coating is less than 5% by weight. In this coated glass plate, if the light transmittance at a wavelength of 500 nm is 90% or more, it is determined to be "compatible", and if it is less than 90%, it is determined to be "incompatible". ``Compatible'' items are visually checked.
It is transparent with no cloudiness, cloudiness, bluishness, or phase separation observed.

The crosslinking agent (ni) in the composition of the present invention is at least one compound selected from amino 6 resins and polyisocyanate compounds.

The above amino resins typically include amine group-containing compound components such as melamine, urea, acetaguanamine, benzoguanamine, spiroguanamine, and steroguanamine, and aldehyde compound components such as formaldehyde, paraformaldehyde, acetaldehyde, and glyoxal. Condensation reaction products obtained by reacting with and by a method known per se; or melamine resins, urea resins, benzoguanamine resins, etc. obtained by denaturing the condensate obtained in this way with alcohol, and are commonly used in paints. You can use any one that is commonly used for this purpose. Among these, preferred are those obtained by partial or complete etherification with C1-C alcohols.

Specific examples of the above-mentioned melamine resin include hexamethyl etherified methyl melamine, hexabutyl etherified methyl melamine, methyl butyl mixed etherified methyl melamine, methyl etherified methylol melamine, butyl etherified methylol melamine, or 1so-butyl etherified methylol melamine. , or various condensates thereof. Further, as specific examples of the above polyisocyanate compounds, for example,
Aliphatic diisocyanate-1 such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate
・Class: Cycloaliphatic diisocyanates such as xylylene diisocyanate and isophorone diisocyanate; organic diisocyanates themselves such as aromatic diisocyanates such as tolylene diisonanate and 4,4'-diphenylmethane diisocyanate, or each of these Additives of organic diisocyanates and polyhydric alcohols, low molecular weight polyester resins, water, etc.; or polymers of each organic diisocyanate as listed above; furthermore, those having free isocyanate groups such as isocyanate biuret bodies; also free Examples include block 8, which is formed by blocking the isocyanate groups of with a blocking agent. Typical commercially available products with free isocyanate groups include:
"Burnock D-750, -800゜DN-950, -
970 or 1.5-455J (products of Dainippon Ink & Chemicals Co., Ltd.), "Desmodule L, N, HL
or ILJ (product of Bayer, West Germany), "Takenate D-102, -202, ll0N or 11
23NJ (Takeda Pharmaceutical Co., Ltd. product), “Koroi-ni-”
1-L, HL, E H or 203J (product of Nippon Polyurethane Industries Co., Ltd.) or “DuraFut 2/IA-
Examples include 90CXj (manufactured by Asahi Kasei Industries, Ltd.). Blocked polyisocyanate compounds are obtained by blocking using blocking agents known per se, and a typical commercially available product is "Burnock D-550J" (Dainippon Ink Co., Ltd.). Kagaku Kogyo Co., Ltd. product), Takenate B-815-NJ (Takeda Pharmaceutical Co., Ltd. product), Azoitol VX
[-80J (West German Hekiss Co., Ltd. product)], Coronet 1-25074 (Nippon Polyurethane 9 Kogyo Co., Ltd. product), etc. Also, isocyanate ethyl (meth)acrylate, m-impropenyl-α, Polymers of isocyanate group-containing monomers such as α-dimethylbenzyl isocyanate or copolymers of these monomers with other ethylenically unsaturated monomers can also be used as the isocyanate crosslinking agent.

When a curable resin composition is prepared by blending a polyisocyanate compound having free isocyanate groups as a crosslinking agent, this polyisocyanate compound may react with the hydroxyl groups in the polymer particles and the base resin at room temperature. Therefore, it is usually preferable to mix it as a two-component type immediately before use. On the other hand, when a block polyisocyanate compound or an amino resin is blended, it can also be used as a -wave type.

The respective blending ratios of the polymer fine particle dispersion (1), the base resin (ii) and the crosslinking agent (iii) in the curable resin composition of the present invention are (i), (ii) and (ij).
Expressed as a solid content weight ratio in a total of 100 parts by weight, 0 (i) / (ij) / (iii) -2-30/35-
85/10-40, preferably 5-25/45-65/
It can be within the range of 20-40.

The curable resin composition of the present invention thus obtained can be used as it is as a transparent paint, or it can be used as a colored paint by dispersing pigments therein.

Typical pigments that can be added to the curable resin composition of the present invention as necessary include inorganic pigments such as titanium oxide and carbon black; quinacridone pigments and azo pigments. Examples include various organic pigments such as 100% organic pigments, and metal powders such as aluminum powder, copper powder, and zinc powder.

Furthermore, the curable resin composition of the present invention may optionally include:
A curing catalyst can be blended, and various known additives such as various resins, solvents, flow regulators, color separation inhibitors, antioxidants, ultraviolet absorbers, and silane coupling agents can be added. They can also be blended.

1 Among these, examples of curing catalysts include dibutyltin diacetate, dibutyltin dioctate, dibutyltin dilaurate, triethylamine, jetanolamine, etc. when the crosslinking agent is a (block) polyisocyanate compound; When the agent is an amine resin, para-toluenesulfonic acid, phosphoric acid or an alkyl ester of phosphoric acid, or "Beccamin P-198"
(Dainippon Ink & Chemicals Co., Ltd. product) and “NaiCure 1”
Examples include dinonylnaphthalenedisulfonic acid, dodecylbenzenesulfonic acid, and organic amine-blocked products thereof such as 55.2500X, X-49-120, 5225, and 3525J (products of King, Inc., USA).

(Actions and Effects of the Invention) Since the curable resin composition containing the polymer fine particle dispersion of the present invention contains specific polymer fine particles, it does not adversely affect the gloss or smoothness of the coated surface. In particular, it is possible to significantly improve the sagging resistance on the vertical plane and the orientation of the metal flake pigment.

[Examples] Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples.

In Examples and Comparative Examples, "parts" and "%" mean "parts by weight" and "% by weight," respectively.

Example 1 of synthetic leather synthesis of dispersion stabilizer 12-Hydroxystearic acid was dehydrated and condensed under refluxing toluene using methanesulfonic acid as a catalyst to obtain a resin with an acid value of 30.
Condensation was carried out up to. The obtained number average molecular weight was approximately 1.80
Glycidyl methacrylate was added to the terminal carboxyl group of the self-condensing polyester of No. 0 using dimethylaminoethanol as a catalyst to introduce a polymerizable double bond to obtain a solution of macromonomer A-1 with a solid content of 70%. The obtained macromonomer A-1 had about one polymerizable unsaturated double bond per molecule based on the number average molecular weight.

Synthesis Example 2 174 parts of butyl acetate was placed in a 3-7 flask and heated to reflux.Into this, 70% macromonomer A-1 solution 297.0 parts methyl methacrylate 195.9 parts glycidyl methacrylate 18.5 parts xylene
A mixture of 163.0 parts and 9.6 parts of 2.2'-azobisisobutyronitrile was added dropwise at a uniform rate over 3 hours, and the mixture was further aged for 2 hours.

Then, a mixture of 0.05 parts of pt-butylcatechol, 38 parts of methacrylic acid, and 0.5 parts of dimethylamine ethanol was added to the flask, and the reaction was continued at 140°C for about 5 hours until the resin acid value reached 0.5. A macromonomer A-2 solution with a solid content of 50% was obtained. The obtained macromonomer A-2 is P-12
A graft polymer having a first segment formed by ISA and a second segment formed from a copolymer of methyl methacrylate and glycidyl methacrylate, with an average of about 4 polymerizable unsaturated double bonds per molecule. had.

Combination Example 3 1.00 parts of xylene was heated to 130° C. in a reaction vessel, and a mixture of the following monomer and polymerization initiator was added dropwise over 3 hours, followed by aging for 2 hours after the addition.

2-ethylhexyl methacrylate 50 parts n-butyl methacrylate 33 parts 2-hydroquine ethyl methacrylate 15 parts methacrylic acid
2 parts 2.2'-azobisisobutyronitrile 2 parts The resulting acrylic resin varnish has a solid content of 5
0%, and the number average molecular weight was 7,000.

To 202 parts of the acrylic resin varnish obtained above, 1 part of glycidyl methacrylate, 4-tert, -
0.022 parts of butylpyrocatechol and 0.1 parts of dimethylamine ethanol were added and stirred at 130°C for 5 hours to introduce a copolymerizable double bond into the molecule to obtain a macromonomer B solution. The number of introduced double bonds in macromonomer B was approximately 1.0 per molecule based on the number average molecular weight. Furthermore, macromonomer B has an SP value of 8°40 and a hydroxyl value of 64.7 mgKOH/g.

Production of polymer fine particle dispersion Production example 1 70% macromonomer A-1 solution 14.3 parts 50%
Macromonomer B solution 46.0 parts to butane
Pour 197.0 parts into a flask,
A mixture of the following monomer and polymerization initiator was added dropwise over 5 hours at reflux temperature, and the mixture was aged for 4 hours to obtain a polymer fine particle dispersion (I).

Styrene 10 parts Methyl methacrylate 55 parts Methyl acrylate 10 parts Acrylonitrile
5 parts 2-hydroxyethyl acrylate
15 parts glycidyl methacrylate 2s
Methacrylic acid 3 parts 2.2'-
2 parts of azobisisobutyronitrile 6 parts of dimethylaminoethanol 0.1 part The obtained dispersion (I) was a white dispersion with a solid content of 40%. The particle size of the dispersed particles was approximately 270 μm (peak particle size).

Measurement of particle size is done using Coulter Counter's CULTE.
This was carried out using a quasi-elastic light scattering method using the RW-4 model. Hereinafter, the particle diameter was measured according to this method.

Furthermore, the dispersed particles were insoluble in either acetone or ethyl acetate, confirming that the particles were crosslinked.

Production Example 2 50% Macromonomer A-2 solution 30 parts 50% Macromonomer B solution 70 parts Hebutane
175 parts were charged into a flask, and a mixture of the following monomer and polymerization initiator was added dropwise at reflux temperature over 5 hours.
Aging was performed for 2 hours.

Methyl methacrylate) 61 parts n-butyl acrylate 20 parts 7 acrylonitrile 2 parts methyl acrylate 5 parts 2-hydroxyethyl acrylate 10 parts m-impropenyl-α,
σ-Dimethylbenzyl isocyanate 2
Part: t-butyl peroctoate: 2 parts: The obtained fine polymer particle dispersion (II) was a white dispersion having a solid content of 40%. The particle size of the dispersed particles was about 250 nm as a peak particle size.

Furthermore, the dispersed particles were gelled fine particles that were insoluble in either acetone or ethyl acetate.

Note that m-impropenyl-α,σ-dimethylbenzyl isocyanate was separated from 2-human kilooxyethyl acrylate and supplied from a separate dropping funnel.

Production Example 3 Production Example 2 was carried out in the same manner as Production Example 2, except that the following mixture was used as the mixture of the monomer and polymerization initiator to be dropped, and the aging time after the mixture was dropped was 4 hours. Polymer fine particle dispersion 8 liquid (III) was obtained.

Styrene 25 parts Methyl methacrylate 62 parts Acrylonitrile
2-part methyl methacrylate
5-part glycidyl methacrylate
2 parts acrylic acid 4 parts 2 parts
．． 2'-Azobisisobutyronitrile 1.5 parts Dimethylaminoethanol 0.1 part The obtained dispersion (II[) was a white dispersion with a solid content of 40%. The particle size of the dispersed particles was about 240 nm (peak particle size), and the particles were gelled fine particles insoluble in either acetone or ethyl acetate.

Production Example 4 In a flask, 175 parts of heptane 50% macromonomer A-2 solution 20 parts 50% macromonomer B
30 parts of the solution was charged, and the following mixture was added dropwise at reflux temperature over 5 to 9 hours, followed by aging for 2 hours to obtain a polymer fine particle dispersion (IV).

50% macromonomer A-2 solution 20 parts 50% macromonomer B solution 30 parts Styrene
20 parts methyl methacrylate
60 parts 2-human kilooxyethyl acrylate
15 parts glycidyl methacrylate 1.5 parts acid phosphooxyethyl methacrylate 1.5 parts 2.2'
-Azobisisobutyronitrile 2 parts of the resulting dispersion (
IV) was a white dispersion with a solids content of 40%. The particle size of the dispersed particles is approximately 210 μm (peak particle size),
Furthermore, these particles were gelled fine particles that were insoluble in either acetone or ethyl acetate.

Note that glycidyl methacrylate was separated from acid phosphooxyethyl methacrylate and supplied from a separate dropping funnel.

Production Example 5 (for comparison) 0 50% macromonomer A-2 solution in flask 6 parts methyl methacrylate 10 parts hebutane
After charging 172 parts and 0.2 parts of 22'-azobisisobutyronitrile and reacting at reflux temperature for 1 hour, the following mixture was added dropwise over 5 hours to react, and further aged for 4 hours to form a polymer. Obtain fine particle dispersion (V)
child .

50% macromonomer A-2 solution 24 parts methyl methacrylate 98 parts glycidyl methacrylate 1 part methacrylic acid
1 part 2.2'-azobisisobutyronitrile 1 part dimethylaminoethanol 0.1 part The obtained dispersion (V) was a white dispersion with a solid content of 40%. The particle size of the dispersed particles was about 300 nm (peak particle size), and the particles were gelled fine particles insoluble in any solvent such as acetone or ethyl acetate.

1 Production Example 6 (for comparison) 50% macromonomer B solution in flask 50 parts hebutane
150 parts Kinren
After charging 25 parts and raising the temperature to reflux temperature,
The following mixture was added dropwise at a uniform rate over 5 hours, and then aged for 4 hours to obtain a polymer fine particle dispersion (Vl).

50% macro 7mer B solution 50 parts methyl methacrylate 96 parts glycidyl methacrylate 2 parts methacrylic acid
Part 2 2.2'-Azobisisobutyronitrile
1.5 parts dimethylaminoethanol 0.1
The resulting dispersion (VI) was a white dispersion with a solid content of 40%. The particle size of the dispersed particles was about 250 nm (peak particle size), and the particles were gelled fine particles insoluble in either acetone or ethyl acetate.

Production of base acrylic resin solution 2 Production example 7 75 parts of xylene and butyl acetate in a flask
A mixture of the following monomer and polymerization initiator was added dropwise at a uniform rate over 4 hours at 11O'o, and then heated for 1 hour to form a transparent acrylic resin solution A with a solid content of 50%. I got it.

Styrene 10 parts n-butyl methacrylate 20 parts n-butyl acrylate 18 parts 2-ethylhexyl methacrylate 30 parts 2-hydroxypropyl acrylate 20 parts acrylic acid 2 parts t
-Butyl peroctoate 4.5 parts The obtained acrylic resin has a number average molecular weight of approximately 42,000 and a hydroxyl value of 35.
mgKOH/g resin, sp value was 8°73. Further, this resin was incompatible with macromonomers A-1 and A-2, but was compatible with macromonomer B.

3 Production Example 8 (for comparison) A transparent acrylic resin solution B with a solid content of 50% was obtained in the same manner as Production Example 7 except that the following mixture was used as the mixture of monomer and polymerization initiator.

Styrene 20 parts Methyl methacrylate 58 parts 2-hydroxyethyl methacrylate 20 parts Acrylic acid
2 parts t-butyl peroctoate
4.5 parts of the obtained acrylic resin has a number average molecular weight of about 8.0
001 hydroxyl value was 86 mgKOH/g and SP value was 9.6. Further, this resin was incompatible with either macromonomer AL A-2 or B.

Examples 1 to 4 and Comparative Examples 1 to 4 The formulations shown in Table 1 below were stirred and mixed, and then mixed with aromatic petroleum solvent Pegasol 150 (manufactured by Mobil Oil Co., Ltd.) at a viscosity of 30 seconds/Ford Cup #4.20. A clear paint was obtained by adjusting the temperature to °C.

Test method 4: Kansai Paint Co., Ltd.'s metallic base coat "Magiclon Base (silver metallic color)" total dry film thickness of 18 μm on steel plate coated with cationic electrodeposition and intermediate coating.
After air spray painting was carried out in two parts to give a dry film thickness of 40 μm, the clear paint was applied again to give a dry film thickness of 40 μm. Then, after setting it at room temperature for about 9 minutes, it was heated to 140'C in a hot air electric furnace!
It was heated and cured for 30 minutes.

The clear paint was applied on horizontal and vertical surfaces, and heated and cured in an electric furnace while maintaining the horizontal and vertical surfaces. About this painted board Vertical surface gloss,
Horizontal surface gloss and horizontal surface finish appearance were investigated. The finished appearance on the horizontal surface was evaluated according to the following criteria.

×: Poor visual gloss and smoothness.

○: Good gloss and smoothness by visual inspection.

Regarding the vertical surface sagging level, in the coated plate preparation method using the above test method, clear paint was sprayed so that the film thickness (cured film) from the left end to the right end in the longitudinal direction of the steel plate varied continuously from 250 μm to 60 μm. Coated plates were obtained in the same manner except that they were coated with a gun and heated and cured by standing vertically, and evaluation was made based on the maximum clear film thickness (cured film) that did not cause sagging.

×: Maximum clear film thickness is less than 35 μm △: Maximum clear film thickness is 35 to 45 μm ○: Maximum clear film thickness exceeds 45 μm 6

Claims (1)

[Claims] 1. A macromonomer (A) containing a molecular chain of poly(12-hydroxystearic acid) and having an average of about 1 or more polymerizable unsaturated double bonds per molecule; A copolymer of ethylenically unsaturated monomers, with a solubility parameter (SP value) of 7.5 to 9.2 and an average of about 1.0 to about 1.5 monomers per molecule. At least two vinyl monomers each having complementary functional groups that can react and bond with each other in the presence of a mixture with a macromonomer (B) having a polymerizable unsaturated double bond. a vinyl monomer mixture containing at least 0.5% by weight of each;
The macromonomer (A), the macromonomer (B), and the vinyl monomer mixture are dissolved, but the polymer formed from the vinyl monomer mixture is not substantially dissolved in the copolymerization and A dispersion of gelled polymer fine particles subjected to a crosslinking reaction. 2. The macromonomer (A) is a polymerizable unsaturated group-containing reaction product obtained by adding an epoxy group-containing polymerizable unsaturated compound to the terminal carboxyl group of poly(12-hydroxystearic acid), which has an epoxy group. It is obtained by adding a polymerizable unsaturated carboxylic acid to a copolymer containing pendant epoxy groups obtained by graft copolymerization or block copolymerization with a polymerizable unsaturated monomer mixture containing a polymerizable monomer. The gelled polymer fine particle dispersion according to claim 1, which is a macromonomer having 1 to about 10 polymerizable unsaturated double bonds. 3. The gelled polymer fine particle dispersion according to claim 2, wherein the epoxy group-containing polymerizable unsaturated compound is glycidyl methacrylate, and the polymerizable unsaturated monomer mixture is mainly composed of methyl methacrylate and contains glycidyl methacrylate. liquid. 4. The macromonomer (A) is formed by adding an epoxy group-containing polymerizable unsaturated compound to the terminal carboxyl group of poly(12-hydroxystearic acid), and has about one polymerizable unsaturated double bond in one molecule. The gelling polymer fine particle dispersion according to claim 1, which is a macromonomer having a macromonomer comprising: 5. Macromonomer (B) has a number average molecular weight of 3000 to 2
0000 and hydroxyl value 45-150mg・KOH/g
The gelling polymer fine particle dispersion according to claim 1, 2, 3, or 4, which has the following. 6. Claims 1, 2, 3, 4, or 6, wherein the combination of complementary functional groups is selected from epoxy group/carboxyl group, alkoxysilyl group/hydroxyl group, epoxy group/phosphoric acid group, and isocyanate group/hydroxyl group. 5. The gelled polymer fine particle dispersion according to 5. 7. (i) the gelled polymer fine particle dispersion according to claim 1; (ii) a substrate forming a continuous phase that is incompatible with the macromonomer (A) but compatible with the macromonomer (B); A curable resin composition containing a resin and (iii) at least one crosslinking agent selected from amino resins and polyisocyanate compounds. 8. The curable resin composition according to claim 7, wherein the gelled polymer fine particle dispersion (i) is the gelled polymer fine particle dispersion according to claim 2. 9. Base resin (ii) has a number average molecular weight of 3000 to 500
9. The curable resin composition according to claim 7, which is an acrylic resin having a solubility parameter (SP value) of 0.00, a solubility parameter (SP value) of 7.5 to 9.5, and a hydroxyl value of 45 to 170 mgKOH/g.